Process for the production of acrylonitrile



June 15, 1965 M. c. BAKER PROCESS FOR THE PRODUCTION OF AGRYLONITRILE Filed Jan. 10, 1962 w v w 2533 :25 .2

MELVIN C. BAKER TAR CONCENTRATION AS PERCENT BY WEIGHT 0F GATALYST SOLUTION BY WWZM United States Patent 3,189,642 PRQCESS FOR TEE PRQDUCTION (3F ACRYLGNITRILE lv lelvin C. Baker, Lewiston, N.Y., assignor to E. 1. du Pont de Neniours and Company, Wilmington, Del., :1 corporation of Delaware Filed Jan. 10, 1962, Ser. No. 165,400 4 Claims. (Cl. 2d0465.3)

This invention relates to the production of acrylonitrile by the reaction of hydrogen cyanide and acetylene in a non-aqueous liquid catalyst, and is more particularly concerned with improvement of anhydrous cuprous chloride catalyst solutions for producing acrylonitrile.

The liquid phase production of acrylonitrile is known to require a large investment in equipment. For economical production it is important to obtain high productivity from this equipment. Productivity will be evaluated herein as pounds of acrylonitrile produced per day per cubic foot of catalyst solution, and will be referred to as spacetime-yield (STY). It is also important to minimize byproduct formation, both to obtain high yields of acrylonitrile and to reduce the amount of unwanted material which must be separated, and disposed of, in the process. Aqueous solutions of cuprous chloride catalyst have commonly been used in the liquid phase process for producing acrylonitrile from acetylene and hydrogen cyanide. Nonaqueous catalyst solutions have recently received attention as a way of reducing the formation of unwanted byproducts. These do avoid the formation of certain volatile by-products, such as acetaldehyde and lactonitrile, but difiiculties with other lay-products have remained. Nonvolatile by-products have been particularly troublesome, as these accumulate in the reactor and seriously reduce the space-time-yield, unless regularly removed. This complex black mixture of non-volatile by-products solidifies upon cooling and is commonly designated tars.

Cuprous chloride as such is substantially insoluble in water, so the aqueous catalyst solutions are prepared by forming a soluble cuprous chloride complex with an inorganic salt or organic amine. This is also true of most non-aqueous cuprous chloride catalyst solutions. However, Burris, Sheard and Vines found that cuprous chloride can be dissolved directly in organic nitriles without added solubilizer to form more etfective catalyst solutions, as disclosed in their US. Patent No. 2,920,098, issued lanuary 5, 1960. The class of organic nitriles is believed to be unique in this respect and to provide a distinct catalyst system containing a new form of active catalyst. Solubilizer salts of the prior art were found to be detrimental. Or anic amines greately increased the proportion of tars formed, and inorganic salts which are substantially insoluble in the new catalyst system form separate phases that clog the reactor. I

Although amines are objectionable in the new cuprous chloride-organic nitrile actalyst system, the chemically related class of carboxamide compounds are surprisingly effective promoters for this catalyst system, as disclosed in Rowbottom US. Patent No. 2,999,072 and Harris US. Patent No. 2,999,073, both issued September 5, 1961.

These carboxamides are not solubilizers for cuprous chloride. In fact, they lower the concentration of catalyst which can be present in solution, but this does not become serious until the solution contains more than 30 percent of carboxamide and only about 0.2 to percent is needed as a promoter. As disclosed in the above patents, the carboxamides greately increase the space-time-yield of acrylonitrile and lower the proportion of tar produced.

The dialkylformamides are especially efiective in both respects when used as the promoter in amounts of about 1 to 10 percent by weight of the catalyst solution.

djdgfidz Patented June 15, 1965 It is an object of this invention to provide a further improvement in the above promoted non-aqueous cuprous chloride catalyst compositions and process for producing acryonitrile. Another object is to increase the productivity of acrylonitrile obtained with the promoted anhydrous cuprous chloride catalyst solution and also obtain a still more favorable ratio of acrylonitrile to tars produced. Other objects will become apparent from the specification and claims.

In accordance with the present invention, acrylonitrile is produced at high productivity and yield by reacting acetylene with hydrogen cyanide at -150 C. in a nonaqueous liquid reaction medium comprising at least 5% of cuprous chloride dissolved in an organic nitrile as the essential component for dissolving the cuprous chloride, and promoted with 0.2% to 30% of carboxamide compound and 0.001% to 0.6% of a silver salt basedon the weight of liquid reaction medium. The organic nitrile and the carboxamide should have boiling points of at least 100 C. at atomspheric pressure, and be thermally stable at 100 C., to avoid excessive losses from the catalyst solution at the temperature used to produce and vaporize theacrylonitrile, which is most readily recovered as condensate from reaction elf-gases. The catalyst solution is preferably maintained acid in continuous operation by introducing hydrogen chloride in an amount between about 1% and 20% by weight of the hydrogen cyanide used. The concentration of by-product tars must be controlled by catalyst replacement, either continuously or intermittently at suitable intervals. The concentration of tars may range from about 2% to about 20%, and should preferably be Within the range of 5% to 15% by weight of the liquid reaction medium. Since the presence of water contributes to by-product formation, the liquid reaction medium is preferably kept substantially anhydrous by the use of technically dry feeds of acetylene, hydrogen cyanide and hydrogen chloride, as well as materials used in making up the reaction medium.

The proportions of acetylene and hydrogen cyanide may be varied over a wide range. Molar gas ratios of C H to HCN in the range of 25: 1 to 2:1 are suitable. High ratios are ordinarily undesirable because of the expense of recovering the large amount of unreacted acetylene and recycling it to the process. Low ratios give lower space-tirne-yields. The most efiicient operation is usually at molar ratios in the range of 15: 1 to 6:1.

Increasing the rate at which reactants are feed to the reaction medium will increase the space-time-yield until the maximum STY is reached, when further increases merely provide increasing amounts of unreacted feed in the off-gas. Preferably a total flow rate is used which will provide a slight excess of hydrogen cyanide and, of course, a considerable excess of acetylene in the reaction oil-gas.

Temperatures of about 120 C. and substantially atmospheric pressure are usually best for the reaction. In general, higher temperatures or higher pressures give higher space-time-yields of acrylonitrile but are less favorable with respect to the ratio of acrylonitrile to byproducts; lower temperatures give lower space-time-yields and increase the difiiculty of maintaining a fluid, homogeneous liquid medium containing a high concentration of cuprous chloride catalyst. The temperatures should be high enough to vaporize the acrylonitrile product, which boils at 78 C. under atmospheric pressure. Lower pressures can be used, but the additional expense of vacuum operation usually makes this undesirable.

increasing the concentration of cuprous chloride catalyst in solution usually results in correspondingly higher spacetime-yields without adverse effect on the acrylonitrile to by-prod'uct ratio. Preferably the catalyst solution is substantially saturated with cuprous chloride. However, as

discussed in US. Patent No. 2,999,072, as little as 5% silver salt inthe catalyst solution.

7 presence or absence'of silversalt activator.

by weight cuprous chloride may be desirable for special purposes. e V

In the. drawing, which is a. graphical illustration of typical acrylonitrile production rates (STY) as attraction of the amount of tar present in the Catalyst solution, for operation under the. above conditions;

Curve 1 shows results when operating in accordance with this invention with a'catalyst solution or" cuprous chloride in organic nitrile' containing silver salt and carboxamide compound, V e v Curve 2 shows results when operating in accordance with this invention under comparable conditions, but with a smaller amount of silver salt in solution, a Y Curve 3 shows, for comparison, the efi'ectof omitting the silver salt under otherwise comparable conditions, and Curve 4 shows, for comparison," the efiect of omitting the carboxarnide compound under conditions otherwise 7 comparable to .those'for curve 1.

As illustrated by curves land 2, the presence of silver salt in addition to the amide promoter makespo'ssible'an unexpectedly great increase in productivity in comparison with the'productivity of catalyst solutions differing only in containing no. silver salt, curve 3)]: The productivity I a or" the former ismore sensitive to the concentration of tar present than the latter; fortunately, the best results are obtained within the range of 5 to vby weighttar in solution, a range which approximates that founddesirable forother reasons in continuous operation. The above improvement is even more surprising whencornpared with resultsobtained when no amide promoter is present '(curve 4), since the silver salt then has no appreciable effect. The silver salt is not a promoter, but has some other eifectin'the catalyst system, and will be referred .to as an activator.

Trace amounts of silver salt will provide some .im-

provement-and10.001% by weight of the catalyst solution is sufficient for activation. Since silver is relativelyexpensive and'dificult to-recover from; used catalyst, and amounts greater than ,6%. by Weight are unnecessary, this is a practical upper limit.

7 7 Highly effective activation is obtained in the rangeof 0.01% to 0.1% by weight of Due to the hydrogen cyanide and hydrogen chloride 'fed into the solution, the silver salt is apparently present as a cyanide or chloride ,salt even though another silver salt is supplied, so a Wide variety or" silver saltscan be added.' Accordingly, reference hereinafter to the silver salt as either silver chloride or silver cyanide is not liinitative as to the form of salt before it is dissolved in the catalyst solution. r

. -Reierence has been made tothe drawing to show the improvement in acrylonitrile production rate provided by a the presence of silver salt activator. There is a corresponding improvement in the. ratio of acrylonitrile product. to tar formed." Under the conditions of curves 1, 2

and 3, the'tar concentration increased linearly as afunction of time at substantially the same rate in eachcase.

.With 5% of dimethylformamide promoter present, the concentration of tar reaches in about 160 hours in the absence of catalyst replacement, independently of the However, the tar rate in pounds per day per cubic foot of catalyst solution increases linearly with the concentration of amide promoter used, whereas the acrylonitrilerate reaches a maximum at about 8% to 10% of amide promoter in solution. x e 7 These considerations indicate that a concentration of adiponitrile and others of The preferred, amide promoters are substituted role amides having 1 to 3 ofthehydrogens of formamide're placed'by hydrocarbon groups'or", 1 to 10 carbon atoms each and free from aliphatic uns'aturation; the hydrocar bon, group being ,monovalent when substituted on the formamide carbon atoms. Such 'amides include dirnethylformamide, diethylformamide, dipropyltormamides, di-

butyliormamides, N-formylpyrrolidine, 'I'l-io'rmylpiperidine,.N-methylformanilide, acetamide, dimethylac etamide, N-acetylmorpholine, N,Nrdibutylpropionamides,' N,N-dietny toluarnides, benzamides, and their homologs. "Di:

methylformamide. preferred. r V The organic nitrile solvent should boil above the boiling and .diethylformamide' are especially pointof acrylonitrile (78) C. soth at the facrylonitrile Y can readily be separated by distillation; In generaLtor this reason vand in order to avoid excessive loss from the catalyst composition, the organic nitrile should boil above 108 C. at atmospheric'pressure and be relatively stable at I this temperature. It is desirable to use an organichitrile 7 in which cuprous chloride. is sufficiently soluble at 100 C.

.to form solutions containing over- 10% cuprous chloride, 1 and preferably at least 30%,.by weight or the. catalyst composition, since. the concentration of cuprou's chloride in solution hasa' marked effect on the maximum produc:

tion ratewhich can be obtained.

The more desirableyorganic nitriles are thoseof the I general formulas Z wherein A represents hydrogen, methyl, methoxy, halogen, dimethylamino and'cyano substituents, and Y represents a divalent hydrocarbon group of l to 9 total carbon atoms having not more than 4 linear aliphatic carbon atoms in any single carbon chain, such linear carbons being fully saturated. Suitable organic'nitriles include benzonitrile,

,tolunitriles, chlorobcnzonitrile, methonybenzonitrile, fiuo robenzonitrile, phthalonitriles, naphthonitriles, phenylacetonitrile, phenylpropionitrile, phenylbutyronitrile, tetrahydrobenzonitrile, propionitrile, butyronitriles, chloropropionitrile, bromopropionitrile, methoxypropionitrile, di-

methylaminopropionitrile, chlorobutyronitrile, bromobu-. tyronitrile, brornovaleronitrile, succinonitrile, glutaronh trile,..adiponitrile, and methyladiponitrile. Benzonitrile, molecular weight above I OO'are high boiling and are preferred,

" The amount of organic nitrile solvent used should be sufficient to dissolve the cuprous 'chloride, .without'add -L V ing'inorganic salt or salt of aniorganic amine to solubilize about 1% to 10% of amide promoter in the catalyst solution, andpreferably about 2% to'8%, should be used to provide both a high rate of acrylonitrile production and a low relative rate of tar 'iorrnation. Howevenif the rate of tar'tormation is not amajorconsideration', it may bedesirable to use up to 16% or more of amide promoter. .11" the relative rate of tar formation is the primary consideration, it may be desirable to operate with only about 0.2% to 2%- to amide promoter in solution.

the cuprous. chloride, andwill generally be anamount at least equal in weight to the cuprouschloride to be dissolved, but the amount will depend upon the concentration of other components of the catalyst solution.

7 In thefollowing examples, whichillustrate specific embodiments of the invention, components of the lfaction medium are expressed as percentages by weight of the catalyst solution after removal of materials volatile at the reaction temperature used:

. Example 1 A reaction vessel was partially filled withlQOO grams of liquid [reaction medium consisting of 36% cuprous chloride, 59% benzonitrile, 5% dimethylformamide and 0.063% silver chlorides Thereaction medium -was m aintained at 10 0 0, throughout the run to be described',.by'

a' heat transfer jacket surrounding the reaction vessel and 7 provided with'suitable temperature controls.

A mixture of acetylene, hydrogen cyanide and hydrogen chloride wasbubbled through the reaction medium under conditions suchthat the flow of acetylene: was

hours of operation.

maintained constant at 6.4 liters/minute during the run, and the feed of hydrogen chloride was likewise constant at 1.6 liters/hour, but the feed of hydrogen cyanide was varied in accordance with analyses of the reactor off-gas to maintain about 0.4 mol percent HCN in the oil-gas. Under these conditions, the hydrogen cyanide feed rate was from 2% to 3.5% greater than the amount which reacted, and the conversion to acrylonitrile was from 77% to 91%. This corresponds to a ratio of acetylene to hydrogen cyanide in the feed from about :1 upwards, depending upon the rate of hydrogen cyanide feed. Tar was formed at a substantially uniform rate of 2.4 pounds per day per cubic foot of catalyst solution during the run, reaching a concentration of 23.8% in solution after 180 hours. This was ofiset by a decreasing content of benzonitrile, which vaporized slowly into the gases passing through the reactor, so that the weight of reaction medium was maintained substantially constant.

The production rate of acryloni-trile was determined by recovering the acrylonitrile from the reactor elf-gases. The STY, as pounds per day per cubic foot of catalyst solution, started at a low value and increased rapidly .to 60 at 8 hours, 70 at hours, and 85 at 44 hours. A maximum of 90 was reached at 88 hours of operation and then the STY decreased to 80 at 130 hours, 65 at 144 hours and at 180 hours, when the run was terminated.

For purposes of comparison, in a run conducted under the same conditions except that no silver salt was present, the STY rose to at 8 hours and then declined to 50 at 44 hours. It was still 50 at 88 hours, 130 hours and 144 The STY then declined to 45 at 180 hours and 40 at 210 hours, when the run was terminated. The tar rate averaged 2.4 pounds of tar fiormed/day/cu. ft. of catalyst.

Example 2 A run was conducted as in Example 1 with a catalyst solution containing 0.058% silver cyanide instead of the silver chloride of Example 1, and with a constant feed of 8 liters/minute of acetylene. The hydrogen chloride feed was 1.6 liters/hour and the hydrogen cyanide feed was adjusted to provide about 0.25 mol percent HCN in the oil-gas from the reactor. The results were similar to those of Example 1. The STY rose to after 8 hours of operation in this manner, was 73 at 24 hours, 90 at 44 hours, then declined to 80 at 94 hours, at 160 hours, and 40 at 210 hours. The average tar rate was 2.5 pounds/day/cu. ft. of catalyst solution.

For comparison a run was conducted under the same conditions except that the dimethylformamide was omitted from the catalyst solution. This resulted in an STY which was substantially constant at only 5 pounds acrylonitrile/day/cu. ft. of catalyst solution.

Example 3 Example 1 was repeated except that the smaller quantity of 0.016% silver chloride was used in the catalyst solution. The acryonitrile productivity in STY units, as before, was 60 at 8 hours, at 24 hours, at 50 to hours, and then declined with further operation to 63 at hours and 58 at hours, when the run was terminated. The tar rate averaged 2.35 pounds/day/ cu. ft. of catalyst solution.

Example 4 Example 1 was repeated except that the catalyst solution contained 8% dimethyl-formamide instead of 5% of dimethylformamide, and contained only about 0.008% silver salt. A maximum productivity of 85 pounds acrylonitrile/day/ cu. ft. of catalyst solution was reached,

Whereas the maximum obtained without silver salt was 70 STY under these conditions.

Since many diflerent embodiments of the invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited by the specific illustrations except to the extent defined in the following claims.

I claim:

1. In the process for producing acrylonitrile by passing hydrogen cyanide and acetylene through a non-aqueous catalyst solution of cuprous chloride and a carboxamide promoter dissolved in an organic nitrile boiling above 78 C. at atmospheric pressure and thermally stable at 100 C. and maintained acid by addition of hydrochloric acid, the improvement which comprises incorporating a silver salt activator in said catalyst solution and maintaining the weight concentration of by-product tar in the catalyst solution within the range of 2% to 20% by at least partial replacement of catalyst solution said silver salt being present in said catalyst solution as a salt selected from the group consisting of silver cyanide and silver chloride.

2. In the process for producing acrylonitrile by passing hydrogen cyanide and acetylene reactants through a substantially saturated solution of cuprous salt catalyst dissolved in an organic nitrile boiling above 78 C. at atmospheric pressure and thermally stable at 100 C. and maintained acid by addition of hydrochloric acid, the improvement which comprises incorporating in said catalyst soluton 1% to 16% by weight of dialkyl formamide promoter having 1 to 4 carbon atoms in each alkyl substituent and 0.001% to 0.6% by weight of silver salt activator, passing said reactants through the catalyst solution at rates sufiicient to maintain a mol ratio of acetylene to hydrogen cyanide of from 6:1 to 15:1 in the feed and to provide an amount of hydrogen cyanide slightly in excess of the amount which reacts during passage through the catalyst solution, and maintaining the concentration of by-product tar in the catalyst solution within the range of 5% to 15% by weight by partial replacement of catalyst solution said silver salt being present in said catalyst solution as a salt selected from the group consisting of silver cyanide and silver chloride.

3. A process as defined in claim 2 wherein the catalyst solution contains at least 35% by weight of cuproussalt, calculated as cuprous chloride, dissolved in benzonitrile.

4. A process as defined in claim 1 wherein the catalyst solution is a benzonitrile solution substantially saturated with cuprous chloride, contains 2% to 8% by Weight of 'dimethylformamide promoter and 0.01% to 0.1% by weight of silver salt activator, and the average acrylonitrile production rate is maintained in excess of 80 pounds of acrylonitrile per day per cubic foot of catalyst solution by replacement of up to 25% of the catalyst solution per day with fresh catalyst.

References Cited by the Examiner UNITED STATES PATENTS 2,798,882 7/57 Christopher et al. 260465.3 2,798,884 7/57 Christopher et al. 260465.3 2,999,072 9/ 61 Rowbottom 252429 X 2,999,073 9/61 Harris 252429 X OTHER REFERENCES Berkman et al.: Catalysis, 1940, pages 365 and 406.

CHARLES B. PARKER, Primary Examiner. S. H. BLECH, Examiner. 

1. IN THE PROCESS FOR PRODUCING ACRYTONITRILE BY PASSING HYDROGEN CYANIDE AND ACETYLENE THROUGH A NON-AQUEOUS CATALYST SOLUTION OF CUPROUS CHLORIDE AND A CARBOXAMIDE PROMOTER DISSOLVED IN AN ORGANIC NITRILE BOILING ABOVE 78*C. AT ATMOSPHERIC PRESSURE AND THERMALLY STABLE AT 100*C. AND MAINTAINED ACID BY ADDITION OF HYDROCHLORIC ACID, THE IMPROVEMENT WHICH COMPRISES INCORPORATING A SILVER SALT ACTIVATOR IN SAID CATALYST SOLUTION AND MAINTAINING THE WEIGHT CONCENTRATION OF BY-PRODUCT TAR IN THE CATALYST SOLUTION WITHIN THE RANGE OF 2% TO 20% BY AT LEAST PARTIAL REPLACEMENT OF CATALYST SOLUTION SAID SILVER SALT BEING PRESENT IN SAID CATALYST SOLUTION AS A SALT SELECTED FROM THE GROUP CONSISTING OF SILVER CYANIDE AND SILVER CHLORIDE. 